Abstract
In this study, gel membranes of chitosan-g-poly(ethylene glycol) dimethacrylate (CS-g-PEGDMA) with pH sensitive properties were synthesized without employing any photo-initiator and crosslinker. First, CS was endowed with UV-sensitive property by reaction with cinnamoyl chloride in methanesulfonic acid. The reaction mainly occurred on the hydroxyl groups of the pyranose unit, while most C-2 amino groups were protected. The substitution degree of cinnamoyl group was 0.98, while the protection efficiency of –NH2 was about 80 %. Upon UV-irradiation, initial free radicals were produced only along the cinnamoyl-modified CS chains, which induced the grafting of PEGDMA from the chitosan chains and eventually the crosslinking. Increasing the feeding amount of PEGDMA increased the grafting ratio as well as the crosslinking density. The Tg value decreased from 161 °C for the pure chitosan to about 90 °C for the CS-g-PEGDMA with a grafting ratio of 1.29. Two stages of degradation correspondent to the individual degradation of CS chains and the PEGDMA chains were observed for all CS-g-PEGDMA copolymers, demonstrating their nature of graft copolymers. The tensile mechanical properties of the CS-g-PEGDMA membranes were affected by the two opposing factors: inter-connected soft PEGDMA chains and crosslinking density; and the optimum properties were achieved when the grafting ratio was increased to about 0.80. By combining CS and PEGDMA components, these copolymer membranes thus have the potential to be used as biomedical membranes.
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References
Adali T, Yilmaz E (2009) Synthesis, characterization and biocompatibility studies on chitosan-graft-poly(EGDMA). Carbohyd Polym 77:136–141
Badawy MEI, Rabea EI, Rogge TM, Stevens CV, Smagghe G, Steurbaut W, Höfte M (2004) Synthesis and fungicidal activity of new N, O-acyl chitosan derivatives. Biomacromolecules 5:589–595
Bhattarai N, Ramay HR, Gunn J, Matsen FA, Zhang M (2005) PEG-grafted chitosan as an injectable thermosensitive hydrogel for sustained protein release. J Control Release 103:609–624
Colonna C, Conti B, Perugini P, Pavanetto F, Modena T, Dorati R, Iadarola P, Genta I (2008) Site-directed PEGylation as successful approach to improve the enzyme replacement in the case of prolidase. Int J Pharm 358:230–237
Don TM, Chou SC, Cheng LP, Tai HY (2011) Cellular compatibility of copolymer hydrogels based on site-selectively-modified chitosan with poly(N-isopropyl acrylamide). J Appl Polym Sci 120:1–12
Ganji F, Abdekhodaie MJ (2010) Chitosan–g-PLGA copolymer as a thermosensitive membrane. Carbohyd Polym 80:740–746
Harish Prashanth KV, Tharanathan RN (2007) Chitin/chitosan: modifications and their unlimited application potential- an overview. Trends Food Sci Technol 18:117–131
Hennink WE, van Nostrum CF (2002) Novel crosslinking methods to design hydrogels. Adv Drug Deliv Rev 54:13–36
Heux L, Brugnerotto J, Desbrières J, Versali MF, Rinaudo M (2000) Solid state NMR for determination of degree of acetylation of chitin and chitosan. Biomacromolecules 1:746–751
Hiradate S, Morita S, Sugie H, Fujii Y, Harada J (2004) Phytotoxic cis-cinnamoyl glucosides from Spiraea thunbergii. Phytochemistry 65:731–739
Ishihara M, Ono K, Saito Y, Yura H, Hattori H, Matsui T, Kurita A (2001) Photocrosslinkable chitosan: an effective adhesive with surgical applications. Int Congr Ser 1223:251–257
Li Q, Yang D, Ma G, Xu Q, Chen X, Lu F, Nie J (2009) Synthesis and characterization of chitosan-based hydrogels. Int J Biol Macromol 44:121–127
Lin WJ, Chen MH (2007) Synthesis of multifunctional chitosan with galactose as a targeting ligand for glycoprotein receptor. Carbohyd Polym 67:474–480
Liu L, Li F, Fang Y, Guo S (2006) Regioselective grafting of poly(ethylene glycol) onto chitosan and the properties of the resulting copolymers. Macromol Biosci 6:855–861
Mao S, Germershaus O, Fischer D, Linn T, Schnepf R, Kissel T (2005) Uptake and transport of peg-graft-trimethyl-chitosan copolymer–insulin nanocomplexes by epithelial cells. Pharm Res 22:2058–2068
Ono K, Saito Y, Yura H, Ishikawa K, Kurita A, Akaike T, Ishihara M (2000) Photocrosslinkable chitosan as a biological adhesive. J Biomed Mater Res, Part A 49:289–295
Peng H, Xiong H, Li J, Chen L, Zhao Q (2010) Methoxy poly(ethylene glycol)-grafted-chitosan based microcapsules: synthesis, characterization and properties as a potential hydrophilic wall material for stabilization and controlled release of algal oil. J Food Eng 101:113–119
Rask F, Dallabrida SM, Ismail NS, Amoozgar Z, Yeo Y, Rupnick MA, Radisic M (2010) Photocrosslinkable chitosan modified with angiopoietin-1 peptide, QHREDGS, promotes survival of neonatal rat heart cells. J Biomed Mater Res, Part A 95A:105–117
Rickett TA, Amoozgar Z, Tuchek CA, Park J, Yeo Y, Shi R (2011) Rapidly photo-cross-linkable chitosan hydrogel for peripheral neurosurgeries. Biomacromolecules 12:57–65
Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31:603–632
Sashiwa H, Kawasaki N, Nakayama A, Muraki E, Yamamoto N, Zhu H, Nagano H, Omura Y, Saimoto H, Shigemasa Y, Aiba S (2002) Chemical modification of chitosan. 13. Synthesis of organosoluble, palladium adsorbable, and biodegradable chitosan derivatives toward the chemical plating on plastics. Biomacromolecules 3:1120–1125
Yin R, Wang K, Han J, Nie J (2010) Photo-crosslinked glucose-sensitive hydrogels based on methacrylate modified dextran–concanavalin A and PEG dimethacrylate. Carbohyd Polym 82:412–418
Zhong C, Wub J, Reinhart-King CA, Chu CC (2010) Synthesis, characterization and cytotoxicity of photo-crosslinked maleic chitosan–polyethylene glycol diacrylate hybrid hydrogels. Acta Biomater 6:3908–3918
Zhou Y, Yang D, Ma G, Tan H, Jin Y, Nie J (2008) A pH-sensitive water-soluble N-carboxyethyl chitosan/poly(hydroxyethyl methacrylate) hydrogel as a potential drug sustained release matrix prepared by photopolymerization technique. Polym Adv Technol 19:1133–1141
Acknowledgments
The authors wish to express their appreciation for the financial support from the National Science Council in Taiwan. The authors also want to thank Ms. Ching-Wei Lu in National Taiwan University for the help on the elemental analysis.
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Lin, MC., Tai, HY., Ou, TC. et al. Preparation and characterization of UV-sensitive chitosan for UV-cure with poly(ethylene glycol) dimethacrylate. Cellulose 19, 1689–1700 (2012). https://doi.org/10.1007/s10570-012-9758-5
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DOI: https://doi.org/10.1007/s10570-012-9758-5